William jules samuel grawitz



sulf0-cyanate of anilin.

UN TED STATE PATENT OFFICE.

WILLIAM JULES SAMUEL GRAWITZ, OF NOGENT-SUR-MARNE, FRANCE.

PROCESS OF DYEING.

SPECIFIGATION fOrmiDg part of Letters Patent No. 577,29 3, datedFebruary 16, 1897. Application filed January 18,1895. Serial No.535,347. (No specimens.) Patented in Belgium July 9, 1894, No.110,914;in

Italy January 5,1895, LXXIV, 292 inI'ranOe January 5,

1895.110. 244,121; in Hungary January 10, 1895,11'0. 5,580;

in England February 6, 1895, No. 2,614; in Austria February 10, 1895,N0. 41, and in $pain March 30, 1895,1Io, 16,831.

To all whom it may concern.

Be it known that I,WILLIAM J ULEs SAMUEL GRAWITZ, a citizen of theRepublic of France, residing in Nogent-s ur-Marne, in said Republic ofFrance, have invented certain new and useful Improvements in Processesof Dyeing or Printing Fibers in Black, or Shades Approaching Thereto,(for which Letters Patent were granted to me in Great Britain, No. 2,614, dated February 6,1895; in Belgium, No. 110,914,dated July 9,1894;in Spain,No. 16,831, dated March 30, 1895 in France, No. 244,121, datedJanuary 5, 1895; in Hungary, No. 5,580, dated January 10, 1895; inAustria, N0. 41, dated February 10, 1895, and in Italy, No. LXXIV, 292,dated January 5, 1895,) of which the following is a specification.

This invention relates to an improved process of dyeing or printingvegetable textile fibers, silk, or wool black, or shades approachingthereto, with anilin, its homologues, or

The sulfate of barium isthen separated by filtering and a pure solutionof sulfo-cyanate of anilin-is obtained. The sulfo-cyanate of anilin isalso formed by mixing the nitrate or the hydrochlorate of anilin with asoluble sulfo-cyanate, such as that of barium, calcium, or ammonia; butin these cases the sulfo-cyanate of anilin cannot be separated becausethe nitrates or the chlorids of barium, calcium, or ammonium, which havebeen formed by double decomposition, are themselves soluble like thesulfo-cyanate of anilin; but such a mixture acts practically in the samemanner as the purified and isolated On the contrary, by mixing asolution of a salt of anilin, such as nitrate or hydrochlorate ofanilin, with an insoluble sulfo-cyanate no double decomposition willtake place.

I would have it understood that two or more solublesulfo-cyanates may beused together, similarly that two or moresalts of .anilin maybe employedtogether, for instance,

hydrochlorate of anilin and nitrate of anilin, likewise that vanadate ofammonia may be used conjointly with another soluble vanaderivatives.Fibers which are dyed by means of a salt of anilin (or of one of itshomologues or derivatives) under the oxidizing action of a chlorate (thecolor being developed by aging, that is, byexposing to air inaging-rooms or in aging-machines after drying) are liable to becomeweakened.

The object of the present invention is to overcome this defect byoxidizing the sulfocyanate of anilin instead of the nitrate orchlorhy'drate or other salts already used for the transformation inblack.

The sulfo-cyanate of anilin may be obtained in combining directly thesulfo-cyanic acid (OHNS) with the anilin. It may also be obtained bydouble decomposition. In mixing, for example, a solution ofsulfo-cyanate of barium (ONS) Ba+2H O, with a heated solution of sulfateof anilin, a soluble sulfo-cyanate of anilin and an insoluble sulfate ofbarium are formed according to the following equation:

date. In the same way chlorate of potash may be substituted for chlorateof soda or for any other soluble chlorate, or several may be usedtogether, as well known. I do not confine myself to the use of pureanilin that yields black, as this process is applicable to itshomologues, such as toluidins, xylidins, or derivatives, such asparaphenylenediamin, and in general to all artificial amins known toyield colors approaching black with the decomposition products of thechlorates, whether for printing or for dyeing purposes and whether thematters to be treated are unbleached 0r dyed, in the raw state, spun orwoven, or in course of manufacture.

I will here indicate, merely by way of two examples, the preparation ofthe dye-baths.

First example: Anilin salt, (hydrochlorate or one equivalent,) twelvehundred and ninety-five grams; sulfo-cyanate (soluble) of ammonia,crystallized, or one equivalent, seven hundred and sixty grams; chlorateof soda, or two-thirds of an equivalent containing four equivalents ofoxygen, seven hundred and ten grams.

Second example: Anilin salt, (hydrochlorate,) twelve hundred andninety-five grams;

snlfo-cyanate (soluble) ofamnionia, crystallized, seven hundred andsixty grams; crystallized chlorid of manganese, seven hundred and fiftygrams; chlorate of soda, seven hundred and ten grams.

In both examples the substances are dissolved separately and mixedlukewarm, while I add enough water to make a total volume of thirteenliters, and after cooling I add to the bath one gram of vanadate ofammonia dissolved in one hundred grams of water. The fibrous materialsimpregnated with this mixture take a magnificent black by aging, thatis, by exposing to air in aging-rooms or aging-machines. Byprogressively increasing the proportion of the chlorate as much as sixequivalents of oxygen may be supplied.

I would have it understood that the proportion above indicated may bevaried. I can greatly diminish, for instance, the proportion of thesulfo cyanate, as the sulfocyanate appears to have a specificpreservative action.

In conclusion I would remark that in order to obtain a good color onsilk it is preferable to repeat the dyeing operation two or more times.

The wool chlorinated as indicated by Lightfoot or treated by any otherknown process can be well dyed black with my process.

Having thus described my invention, I claim as new and desire to secureby Letters Patent- The process herein described of dyeing or printingvegetable textile fibers, prepared wool or silk by means of thesulfo-cyanate of anilin or its homologues as set forth, which consistsin treating the fibers with a mixture of a salt of anilin with a solublecyanate capable of forming the sulfo-cyanate of anilin by doubledecomposition, and developing the color by the oxidizing of the chloratein presence of a salt of vanadium, substantially as described.

In testimony that I claim the foregoing as my invention I have signed myname in presence of two subscribing witnesses.

WILLIAM JULES SAMUEL GRAWITZ.

Viitnesses:

GREGORY PHELAN, EDOUARD HENRIGUEZ.

